CN117463007A - Emulsion-type defoaming agent for oil field and preparation method thereof - Google Patents
Emulsion-type defoaming agent for oil field and preparation method thereof Download PDFInfo
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- CN117463007A CN117463007A CN202311424208.1A CN202311424208A CN117463007A CN 117463007 A CN117463007 A CN 117463007A CN 202311424208 A CN202311424208 A CN 202311424208A CN 117463007 A CN117463007 A CN 117463007A
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- defoaming agent
- defoamer
- emulsion
- defoaming
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- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000013530 defoamer Substances 0.000 claims abstract description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 230000001105 regulatory effect Effects 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 26
- 239000010779 crude oil Substances 0.000 description 17
- 239000006260 foam Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 8
- -1 fatty alcohol ester Chemical class 0.000 description 7
- 235000019384 rice bran wax Nutrition 0.000 description 4
- 239000004170 rice bran wax Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 229960002666 1-octacosanol Drugs 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0495—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0422—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing S-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to an emulsion-type defoamer for an oil field and a preparation method thereof. The defoaming agent consists of 1 part of a main defoaming agent, 0.4-0.8 part of triethanolamine, 0.1-0.2 part of sodium dodecyl benzene sulfonate and 2 parts of water; the preparation method comprises the following steps: sequentially adding 1, 3-tetramethyl-1, 3-diphenyl disilazane, methanol, 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride into a reactor, stirring, regulating the pH value, heating and refluxing, distilling under reduced pressure, regulating the pH value, and cooling; adding sodium chloride aqueous solution, sufficiently oscillating, separating liquid, and drying to obtain a main agent of the defoamer; and (3) stirring the main agent of the defoaming agent, triethanolamine, sodium dodecyl benzene sulfonate and water at a high speed, standing, and separating to obtain the product defoaming agent. The defoaming agent has the advantage of good defoaming effect, and the defoaming rate reaches more than 90% when the using concentration is 10 mg/L.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, and particularly relates to an emulsion-type defoamer for an oil field and a preparation method thereof.
Background
During the process of extraction and treatment of crude oil, the temperature rise and the pressure drop can destroy the gas-liquid balance of the crude oil, so that light hydrocarbon dissolved in the crude oil can be changed into gas to escape. However, the light hydrocarbon is difficult to smoothly escape from the surface of the crude oil due to the influence of the viscosity, space, flow and other factors of the oil phase, and bubbles can be formed in the crude oil to cause the volume expansion of the crude oil and generate foam. If crude oil foam cannot be rapidly eliminated, the fluctuation of the whole production flow is easily caused. Therefore, eliminating the foam of crude oil is of great significance in stabilizing the production of crude oil in oil fields.
The method for eliminating the foam from the physical point of view mainly comprises the steps of placing a baffle or a filter screen, mechanically stirring, static electricity, freezing, heating, steam, radiation irradiation, high-speed centrifugation, pressurization and depressurization, high-frequency vibration, instant discharge, ultrasonic waves and the like, and the methods all promote the permeation rate of the gas at two ends of a liquid film and the liquid discharge of a foam film to different degrees, so that the stability factor of the foam is smaller than the attenuation factor, and the quantity of the foam is gradually reduced. However, these methods have the common disadvantages of being more restrictive in terms of environmental factors and not high in defoaming rate.
Methods of eliminating foam from a chemical standpoint mainly include a chemical reaction method and a method of adding an antifoaming agent. The chemical reaction method is to add some reagents to make them react with foaming agent to generate water-insoluble substance, so as to reduce the concentration of surfactant in liquid film and promote the break of foam. The most widely applied defoaming method in various industries at present is a method for adding a defoaming agent, and the method has the greatest advantages of high defoaming efficiency, convenience in use and the like, but is critical to find a proper and efficient defoaming agent.
CN107059474a discloses a higher fatty alcohol emulsion defoamer, which consists of rice bran wax, alkane or vegetable oil, surfactant, thickener, bactericide and water, wherein the rice bran wax is an active ingredient of the emulsion defoamer. The rice bran wax contains higher fatty acid, higher fatty alcohol and higher fatty alcohol ester as main components, and contains a large amount of hexacosanol, octacosanol, triacontanol and their corresponding alcohol esters. The higher fatty alcohol emulsion prepared by rice bran wax is suitable for foam control in each section of pulping and papermaking, and is particularly suitable for foam control of papermaking systems, especially papermaking wet parts. However, the components of the product are too complex, the requirements on the emulsification process are high, the viscosity change is large, and the phenomenon of paste coagulation is easy to occur.
CN115228148B discloses a compound defoaming agent for oil fields and a preparation method thereof, which belong to the technical field of chemical defoaming and comprise the following steps: step 1, preparing modified polysiloxane; step 2: preparing modified silicon dioxide; step 3: adding m-phthaloyl chloride and m-phenylenediamine to perform polymerization reaction to obtain aramid polymerization liquid; step 4, uniformly mixing the modified polysiloxane, the modified silicon dioxide and the meta-aramid polymer solution to obtain a silane compound; step 5, evenly mixing the silane compound and acrylic ester to prepare a complexing agent; and 6, uniformly mixing the complexing agent and the carbon nano tube to obtain the composite defoaming agent for the oil field. The composite defoaming agent for the oil field, which is prepared by the method, is easy to disperse in crude oil, has high defoaming efficiency, can form a layered and dendritic structure by adding meta-aramid fiber, increases the number of cross links between modified polysiloxane and modified silicon dioxide, and improves the stability of foam inhibition. However, the defoaming rate of the invention for 5min is only 90%, and the defoaming effect needs to be further improved.
Disclosure of Invention
The invention provides an emulsion-type defoaming agent for an oil field and a preparation method thereof aiming at the defects of the prior art. The defoaming agent has the advantages of simple preparation process and good defoaming effect.
The invention discloses an emulsion-type defoaming agent for an oil field, which comprises the following components in parts by mass:
the molecular structural formula of the main agent of the defoaming agent is as follows:
the invention further discloses a preparation method of the emulsion type defoamer for the oil field, which comprises the following specific steps:
(1) Sequentially adding 1, 3-tetramethyl-1, 3-diphenyl disilazane, methanol, 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride into a reactor, stirring for dissolution, regulating pH to 3-4 with hydrochloric acid, heating for reflux, distilling off about 80-90wt% of methanol under reduced pressure, regulating pH to 7 with sodium hydroxide solution, and cooling to below 40 ℃;
(2) Adding 10wt% sodium chloride aqueous solution into the reactor, fully oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain a main agent of the defoamer;
(3) And (3) stirring the main agent of the defoaming agent, triethanolamine, sodium dodecyl benzene sulfonate and water at a high speed, standing for 12-24h, and separating out stable emulsion to obtain the product defoaming agent.
In the present invention, it is preferable that the 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride are used in an amount of 0.8 to 1.2 parts by mole and 1 to 1.4 parts by mole, respectively, based on 1 part by mole of 1, 3-tetramethyl-1, 3-diphenyldisilazane; more preferably, the 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride are used in an amount of 0.9 to 1.1 mole parts and 1.1 to 1.3 mole parts, respectively, based on 1 mole part of 1, 3-tetramethyl-1, 3-diphenyldisilazane.
In the present invention, preferably, the mass ratio of the methanol to the 1, 3-tetramethyl-1, 3-diphenyldisilazane in the step (1) is 8 to 10:1.
in the present invention, preferably, the reflux reaction time in step (1) is 1 to 2 hours.
In the present invention, preferably, the mass ratio of the 10wt% aqueous sodium chloride solution to 1, 3-tetramethyl-1, 3-diphenyldisilazane in the step (2) is 6 to 8:1.
the reaction equation for synthesizing the emulsion type defoamer main agent for the oil field is as follows:
the emulsion-type defoaming agent for the oil field has good defoaming function, and the concentration defoaming rate of 10mg/L reaches more than 90%. The main agent of the defoaming agent belongs to a surfactant containing silicon and fluorine, has small surface tension, can replace a foam stabilizer molecule to change the composition and aggregation structure of a film, reduces the viscosity of film liquid, and greatly weakens the strength and elasticity of the film, so that the film is easy to break. The triethanolamine can improve the spreading ability of the main agent of the defoamer, expand the defoaming amount of the whole system, strengthen the stability of the invention, belong to highly branched alcohols and have certain defoaming ability. The sodium dodecyl benzene sulfonate belongs to water-soluble aryl sulfonate, can strengthen the stability of the invention, and has certain defoaming capability. The main agent of the defoaming agent and the triethanolamine contain tertiary amine structures, have certain electropositivity and can strengthen the defoaming effect.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The defoamer has the characteristics of simple preparation process, low cost, no pollution and the like;
(2) The defoaming agent has the advantage of good defoaming effect, and the defoaming rate reaches more than 90% when the using concentration is 10 mg/L.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments:
example 1
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 45.6g of methanol, 16mmol of 2, 3-difluoro-4-aldehyde pyridine and 20mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 1.5 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 34.2g 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 1 ；
(3) 5g of defoamer base Z 1 2g of triethanolamine, 0.5g of sodium dodecyl benzene sulfonate and 10g of water,stirring at high speed, standing for 24 hr, and separating to obtain stable emulsion as defoaming agent X 1 。
Example 2
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 49.8g of methanol, 17mmol of 2, 3-difluoro-4-aldehyde pyridine and 22mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 1h, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 38.8g of 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 2 ；
(3) 5g of defoamer base Z 2 2.4g of triethanolamine, 0.8g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 12h, and separating out stable emulsion to obtain the product defoamer X 2 。
Example 3
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 51g of methanol, 24mmol of 2, 3-difluoro-4-aldehyde pyridine and 28mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 1.2 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 41g of 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 3 ；
(3) 5g of defoamer base Z 3 3g of triethanolamine, 0.7g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 20h, and separating out stable emulsion to obtain the product defoamer X 3 。
Example 4
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 55.7g of methanol, 22mmol of 2, 3-difluoro-4-aldehyde pyridine and 26mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 2 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 44.4g 10wt% sodium chloride water solution into the reactor, oscillating thoroughly, separating liquid, drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 4 ；
(3) 5g of defoamer base Z 4 3.2g of triethanolamine, 0.9g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 16h, and separating out stable emulsion to obtain the product defoamer X 4 。
Example 5
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 57g of methanol, 21mmol of 2, 3-difluoro-4-aldehyde pyridine and 25mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 1.5 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 37.6g of 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 5 ；
(3) 5g of defoamer base Z 5 3.5g of triethanolamine, 1g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 24h, and separating out stable emulsion to obtain the product defoamer X 5 。
Example 6
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 52.3g of methanol, 18mmol of 2, 3-difluoro-4-aldehyde pyridine and 23mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 1.5 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 45.6g of 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 6 ；
(3) 5g of defoamer base Z 6 4g of triethanolamine, 0.8g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 18h, and separating stable milkThe liquid is the product defoamer X 6 。
Example 7
(1) 20mmol of 1, 3-tetramethyl-1, 3-diphenyl disilazane, 55.1g of methanol, 20mmol of 2, 3-difluoro-4-aldehyde pyridine and 24mmol of sodium cyanoborohydride are sequentially added into a reactor, stirred and dissolved, the pH value is regulated to 3-4 by hydrochloric acid, the mixture is heated and refluxed for 2 hours, about 80-90wt% of methanol is distilled off under reduced pressure, the pH value is regulated to 7 by sodium hydroxide solution, and the temperature is reduced to below 40 ℃;
(2) Adding 43.3g of 10wt% sodium chloride aqueous solution into the reactor, sufficiently oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain defoamer main agent Z 7 ；
(3) 5g of defoamer base Z 7 4g of triethanolamine, 1g of sodium dodecyl benzene sulfonate and 10g of water, stirring at a high speed, standing for 24h, and separating out stable emulsion to obtain the product defoamer X 7 。
Test example 1
The defoaming/foam inhibiting properties of defoamers were evaluated with reference to "crude oil defoamer specifications" (Q/SHCG 46-2012).
And taking an oil sample without the defoamer from the crude oil gathering pipeline of a joint station of the victory oil field, and discharging the water at the lower part.
Defoamer X according to the invention 1 -X 7 Distilled water is used to prepare a solution with the concentration of 1.0 weight percent, and the solution is stirred uniformly.
400ml of oil sample is added into a 500ml measuring cylinder, a glass rod is put into the measuring cylinder, and the volume V of the oil sample is recorded 1 . 0.4ml of 1.0wt% crude oil defoamer is added rapidly by a syringe, immediately and rapidly stirred by a glass rod at a stirring speed of not less than 120rpm, stirred for 2min, and the crude oil volume V is observed and recorded 2 。
Adding 1.0wt% crude oil defoamer 1ml into the sample, placing in water bath at 60deg.C, maintaining the temperature for 30min, rapidly stirring with glass rod until the foam of crude oil completely disappears, and reading the volume V of the non-foam crude oil after stirring 3 。
Defoaming rate calculation formula:
X＝(V 1 -V 2 )/(V 1 -V 3 )×100
the oil field defoamer of Shandong Wan Tianhe New Material Co., ltd was used for comparison experiments.
The experimental results are shown in Table 1.
TABLE 1 defoaming Experimental results
| Defoaming agent | Defoaming rate, percent |
| X 1 | 90 |
| X 2 | 92 |
| X 3 | 95 |
| X 4 | 94 |
| X 5 | 96 |
| X 6 | 97 |
| X 7 | 97 |
| Comparative sample | 83 |
As can be seen from table 1: defoamer X of the present invention 1 -X 7 The defoaming rate reaches more than 90 percent when the using concentration is 10mg/L, wherein the maximum defoaming rate reaches 97 percent (X) 6 And X 7 ) And the defoaming rate of the oilfield defoaming agent of the Shandong Wan Tianhe New Material Co., ltd is 83%, which is obviously lower than that of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (7)
1. The emulsion-type defoaming agent for the oil field is characterized by comprising the following components in parts by mass:
the molecular structural formula of the main agent of the defoaming agent is as follows:
2. the method for preparing the emulsion type defoamer for oil fields according to claim 1, wherein the preparation method comprises the following specific steps:
(1) Sequentially adding 1, 3-tetramethyl-1, 3-diphenyl disilazane, methanol, 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride into a reactor, stirring for dissolution, regulating pH to 3-4 with hydrochloric acid, heating for reflux, distilling off about 80-90wt% of methanol under reduced pressure, regulating pH to 7 with sodium hydroxide solution, and cooling to below 40 ℃;
(2) Adding 10wt% sodium chloride aqueous solution into the reactor, fully oscillating, separating liquid, and drying oil phase with anhydrous calcium chloride to obtain a main agent of the defoamer;
(3) And (3) stirring the main agent of the defoaming agent, triethanolamine, sodium dodecyl benzene sulfonate and water at a high speed, standing for 12-24h, and separating out stable emulsion to obtain the product defoaming agent.
3. The method for preparing an emulsion type defoaming agent for oil fields according to claim 2, wherein the amounts of the 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride are respectively 0.8-1.2 mole parts and 1-1.4 mole parts based on 1 mole part of 1, 3-tetramethyl-1, 3-diphenyl disilazane.
4. The method for preparing an emulsion-type defoaming agent for oil fields according to claim 3, wherein the amounts of said 2, 3-difluoro-4-aldehyde pyridine and sodium cyanoborohydride are respectively 0.9-1.1 mole parts and 1.1-1.3 mole parts based on 1 mole part of 1, 3-tetramethyl-1, 3-diphenyldisilazane.
5. The method for preparing the emulsion type defoamer for oil fields according to claim 2, wherein the mass ratio of the methanol to the 1, 3-tetramethyl-1, 3-diphenyl disilazane in the step (1) is 8-10:1.
6. the method for preparing an emulsion type defoamer for oil fields according to claim 2, wherein the reflux reaction time in the step (1) is 1-2h.
7. The method for preparing the emulsion type defoamer for oil fields according to claim 2, wherein the mass ratio of the 10wt% sodium chloride aqueous solution to the 1, 3-tetramethyl-1, 3-diphenyl disilazane in the step (2) is 6-8:1.
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